The Mastcam CCD cameras on the Mars Science Laboratory Curiosity Rover each use an 8-position filter wheel in acquiring up to 1600 × 1200 pixel images. The filter set includes a broadband near-infrared cutoff filter for RGB Bayer imaging on each camera and 12 narrow-band geology filters distributed between the two cameras, spanning the wavelength range 445–1013 nm. This wavelength region includes the relatively broad charge-transfer and crystal-field absorption bands that are most commonly due to the presence of iron-bearing minerals. To identify such spectral features, sequences of images taken with identical pointings through different filters have been calibrated to relative reflectance using pre-flight calibration coefficients and in-flight measurements of an onboard calibration target. Within the first 1000 sols of the mission, Mastcam observed a spectrally diverse set of materials displaying absorption features consistent with the presence of iron-bearing silicate, iron oxide, and iron sulfate minerals. Dust-coated surfaces as well as soils possess a strong positive reflectance slope in the visible, consistent with the presence of nanophase iron oxides, which have long been considered the dominant visible-wavelength pigmenting agent in weathered martian surface materials. Fresh surfaces, such as tailings produced by the drill tool and the interiors of rocks broken by the rover wheels, are grayer in visible wavelengths than their reddish, dust-coated surfaces but possess reflectance spectra that vary considerably between sites. To understand the mineralogical basis of observed Mastcam reflectance spectra, we focus on a subset of the multispectral data set for which additional constraints on the composition of surface materials are available from other rover instruments, with an emphasis on sample sites for which detailed mineralogy is provided by the results of CheMin X-ray diffraction analyses. We also discuss the results of coordinated observations with the ChemCam instrument, whose passive mode of operation is capable of acquiring reflectance spectra over wavelengths that considerably overlap the range spanned by the Mastcam filter set (Johnson et al. 2016). Materials that show a distinct 430 nm band in ChemCam data also are observed to have a strong near-infrared absorption band in Mastcam spectral data, consistent with the presence of a ferric sulfate mineral. Long-distance Mastcam observations targeted toward the flanks of the Gale crater central mound are in agreement with both ChemCam spectra and orbital results, and in particular exhibit the spectral features of a crystalline hematite layer identified in MRO/CRISM data. Variations observed in Mastcam multi-filter images acquired to date have shown that multispectral observations can discriminate between compositionally different materials within Gale Crater and are in qualitative agreement with mineralogies from measured samples and orbital data.